油气田采出水锂资源回收可行性、技术现状及展望

赵紫伊; 周雪; 王铁夫; 李承琛; 孙广东; 孔繁鑫; 杨德敏; 陈进富; 张颖

doi:10.12153/j.issn.1674-991X.20221190

油气田采出水锂资源回收可行性、技术现状及展望

doi: 10.12153/j.issn.1674-991X.20221190

1.
中国石油大学(北京)化学工程与环境学院
2.
北京市碧水源膜科技有限公司
3.
重庆地质矿产研究院页岩气勘探开发国家地方联合工程研究中心

基金项目: 国家自然科学基金面上项目（52270014）；重庆市自然科学基金面上项目（cstc2020jcyj-msxmX0128）

详细信息

作者简介:
赵紫伊 (2001—)，女，研究方向为油气田采出水锂资源回收，2020010389@student.cup.edu.cn

通讯作者:
孔繁鑫(1985—)，男，副教授，博士，研究方向为膜法水处理和石油石化污染控制与资源化技术，kfx11@cup.edu.cn

中图分类号: X741
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出版历程
- 收稿日期: 2022-11-29
- 网络出版日期: 2023-07-19

Feasibility, technical status and prospects of lithium recovery from produced water in oil and gas fields

1.
School of Chemical Engineering and Environment, China University of Petroleum (Beijing)
2.
Beijing Origin Water Membrane Technology Co., Ltd.
3.
National Joint Local Engineering Research Center for Shale Gas Exploration and Development, Chongqing Institute of Geology and Mineral Resources

摘要

摘要:
锂资源高需求低产量的供需矛盾使得开发新的锂资源刻不容缓，而油气田采出水中锂资源丰富，是潜在的液体锂资源，因此分析油气田采出水提锂可行性并提出可行技术路线具有重要的现实意义。首先通过对油气田采出水的组成进行分析，明确了油气田采出水的水质特性；然后对国内主要盆地锂资源禀赋进行分析，强调其复杂的有机-无机高度混杂体系中有机物浓度高且离子组成丰富对提锂的挑战；最后从水质特性、水处理技术和油气田采出水锂资源高效回收技术出发，阐述盐湖提锂技术如沉淀法、膜分离、吸附法、溶剂萃取法和耦合技术对于油气田采出水提锂的适用性。结合提锂实践和产业现状，认为“预处理+富集浓缩（吸附/萃取-膜分离）+沉淀”是可行的提锂技术路线。
- 锂资源提取 /
- 油气田采出水 /
- 可行性分析 /
- 耦合技术
Abstract:
The contradiction between high demand and low production of lithium resources makes it urgent to develop new lithium resources. The produced water of oil and gas fields is rich in lithium elements, which is a potential liquid lithium resource. Therefore, it is of great practical significance to analyze the feasibility of lithium extraction from produced water of oil and gas field and propose a feasible technical route. First, the composition of produced water in oil and gas fields was analyzed, and the water quality characteristics of the produced water in oil and gas fields were defined. Then, the lithium resource endowment of major basins in China was analyzed, and the challenges of lithium extraction due to the high concentration of organic matter and rich ion composition in the complex organic-inorganic hybrid system were emphasized. Finally, the water characteristics, water treatment technology and high-efficient lithium extraction technology were comprehensively analyzed and the applicability of those lithium recovery technologies (precipitation, adsorption, extraction and membrane separation) for produced water was discussed. Combined with the practice of lithium extraction and the current situation of the industry, it was recommended to develop a lithium extraction technical route of "pretreatment + enrichment concentration (adsorption/extraction-membrane separation) + precipitation".
- lithium extraction /
- produced water in oil and gas field /
- feasibility analysis /
- coupling technology

HTML全文

图 1 Eramet的锂提取工艺^[44]

Figure 1. Lithium extraction process by Eramet

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图 2 同时回收锂和去除有机物的电化学系统原理^[55]

Figure 2. Schematic of the electrochemical system for simultaneous lithium recovery and organic pollutant removal

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图 3 Ozone Tek公司耦合提锂系统

Figure 3. Ozone Tek INC coupling lithium extraction system

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表 1 现阶段沉淀法提锂技术特点

Table 1. Characteristics of precipitation lithium extraction technology at present stage

技术名称	沉淀剂	优点	缺点
分步沉淀^[30]	NaOH、Na₂CO₃	流程简单，成本低	吸附共沉淀使锂损失大
改进碳酸化沉淀^[30]	Ca(OH)₂、Na₂CO₃	工艺简单，技术成熟；避免共沉淀损失；可大批量处理卤水	成本高，需加入大量沉淀剂
硼镁、硼锂共沉淀^[31]	硫酸盐、HCl或H₂SO₄	易分离，锂回收率高	成本高
铝酸盐沉淀^[32]	AlCl₃·nH₂O或CaO·Al₂O₃、KOH或NaOH	产品纯度高，回收率高	水耗和能耗大，腐蚀设备

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表 2 常见的无机金属氧化物提锂吸附技术特点

Table 2. Characteristics of lithium adsorption technology for common inorganic metal oxides

吸附剂	吸附原理	适用场景	技术优势	技术局限
铝系吸附剂^[50]	表面自由酸性羟基与Li⁺产生含羟配合物	氯化物/硫酸镁亚型中性（pH为4~7）盐湖卤水	选择性高，成本低，已实现工业化	吸附容量小，在酸性或碱性条件下不稳定
钛系锂离子筛型^[51]	离子交换和位阻效应	碳酸型强碱性（pH>10）盐湖卤水	稳定性好，吸附量大，溶损率低（<0.02%）	合成较困难
锰系锂离子筛型^[52-54]	氧化还原、离子交换和复合反应机制	碳酸盐型盐湖卤水及强碱性（pH>10）盐湖卤水	吸附量大，易制备	吸附过程中溶损率高（约0.1%）

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表 3 常见萃取提锂技术特点

Table 3. Technical characteristics of lithium extraction

萃取剂名称	技术优势	技术局限
有机磷类萃取剂^[58]	选择性高，萃取率达95%	成本高，在萃取过程中溶损严重，对设备强侵蚀，酸性反萃过程中易降解
β-双酮类萃取剂^[59]	萃取率高	协萃剂贵，在碱性条件下溶损严重
冠醚类^[60]	选择性高，易萃取	合成工艺繁杂，价格昂贵
离子液体^[60-61]	化学性质稳定，挥发性低	成本高，制约了工业应用

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表 4 不同提锂技术在液体锂资源中的适用范围

Table 4. Application scope of lithium extraction technology in liquid lithium resources

锂提取技术		适用范围
锂提取技术		Mg²⁺/Li⁺	碱金属离子（Na⁺）	Li⁺浓度/ (mg/L)
沉淀法		低	√	>1 000
吸附法		高	√	>10
膜分离	NF膜法	高	×	10~1 000
膜分离	选择性电渗析法	高	√	200~1 000
注：“高”指Mg²⁺/Li⁺一般高于10的盐湖卤水；“低”指Mg²⁺/Li⁺低的盐湖卤水。√表示该技术适用于含有较高浓度的共存碱金属离子（Na⁺）的盐湖盐水；×表示该技术不适合。

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表 5 提锂技术用于油气田采出水的问题及对策

Table 5. Problems and countermeasures of lithium extraction technology in produced water in oil and gas fields

提锂技术	问题		对策
提锂技术	有机物	共存离子	有机物	杂质离子
吸附法	有机物与金属吸附剂络合造成其吸附能力降低	二价阳离子（Mg²⁺）与Li⁺竞争性吸附	进行预处理，选用高选择性吸附剂	强化预处理，去除杂质离子
溶剂萃取法	有机物抑制萃取作用	二价阳离子和碱金属离子（Na⁺）与Li⁺竞争萃取	使用非氟化离子液体，进行多阶段萃取	使用非氟化离子液体，进行多阶段萃取
膜分离	有机物会造成严重的膜污染，降低使用寿命	碱金属离子（Na⁺）与Li⁺竞争通过膜，造成膜的选择性下降	进行预处理，发展抗污染膜	强化预处理，提高膜选择性
沉淀法		二价阳离子（Mg²⁺）浓度高，除杂沉淀剂消耗量大，碱金属离子（Na⁺）竞争沉淀	强化预处理，去除杂质离子	与膜基技术、溶剂萃取法或吸附法耦合

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